Medium for bleaching, cracking, and desulphurizing petroleum and other hydrocarbon compounds and process of preparing same



Patented Jan. 19,1926.

UNITED STATES I 1,570,005 PATENTQFFI v nnnmonn rmeo nnmsonn, or om'a nmnnsaasxa; earn nu'oo some assrenoa ro sem Imam anmnoan.

' more]: non :auacnmo, caacxma, Ami pnsunr'nuarznre rnraonntru OTHERCOMPOUNDS AND PROCESS OI PREPARING BAKE.

Il'o Drawing.

To'aZZ whom itmwy concern:

Be'it known that we HERMAN.REINBOLD and HUGO Rnmnono, both .citizens ofthe United States of America, residing t Omaha, in .the county ofDouglas and ate of Nebraska, have invented certain new and usefulImprovements in Mediums for Bleaching, Cracking, and Desulph-urizingPetroleum and Other Hydrocarbon Compounds and Processes of PreparingSame, of which the following is a specification.

This invention relates to the'useof clay, especially-a colloid-clay ofthe bentonite type, as. a'medium for refining and distilling oils and tothe processes of preparing-and using the same.

The use of anhydrous aluminum chloride has been ractised in the refiningof petroleum' an other oils. The high cost and its ' ininum chloride;

limitedsupply thereof, has, however, made neral use impracticaL- heobjects of the present invention are:

' To provide a source of supplyfor the alu- To provide ahighl stance orbase in whic' the aluminum chloride is heldin colloidal dispersion so asto present amaximum active surfacefor reaction on the hydrocarbons; I

' To rovidein addition to'the porous base and a uminum chloride anadditional catalyst. which will raise the volatilizing temperature ofthe aluminum chloride "so that oils, such as-shale oils and-high asphaltcontent oils, which are volatile only at temperaturesabove that ofaluminum chloride may be treated;

To provide a porous colloidal basefor either or both thealuminumchloride and the additional catalyst which will in itself be an activeagent in the oil refinin piaocess. Other objects and advantages wil comeapparent in the preparation of the product 5 and in its use as an oiltreating medium and itlis desired to be understood that all such.

, objects and advantages are anticipated and within the spirit of thisinvention.

infiltrationor other causes,due to'the gee porous, active subheld incolloidal an Application and 1mm 21, 1924. sci-n1 Io. 68'l,654

logical conditions under which they were formed. The process isalso-applicable to .all solid alumino-silicates which are capable ofbeing converted into the hydrous variety .by chemical treatment.

Our new oil treatingfcom'poiind or medium is prepared for use by thefollowing varying from 4 to 7 mesh.

( Wetting. The ground bentoiiite issoakedin water suflicient only-topenetrate,

all of the pores ofthe mineral without forming a v jelly. Bentonitengsexplained in our co-pending application filed Oct. 18, 1923). is a verycolloidal clay rial Nof 66 9,306,

ste s: 4 g 7 8r) Grinding. The clay is groundIto size and has theproperty of swelling to a jellylike mass of greatly increased volumeupon Therefore, in this step caremust be taken-to add only enough. i i

the addition of water.

water to fill the pores without causing it to;

jelly and destroy itsoriginal structure and. shape;

The water is added for the Eur of re-; ducing the concentration of t eydroehlm ric acid and preventing the destruction of the structure of theclay by toorapidland violent action.

(a) Chlorination. Approximately '90 per ydroch-loric (acid. (H01) isslowly and gradually added to cent of P concentrated the wet'mineralwhile it is being stirred and agitated. Because of the greatersolubilityof the hydrochloric acid at a low temperar 'ture this step is carried onat ordinaryrjoom temperature. The mixture" is now allowed to stand forfrom 10 to-12 hours. Bentonite is an hydra-ted aluminum-silicatecontaining",

in its natural state from 20 to per cent alumina, someinfiltratedimpurities such as lime, magnesia, iron ete., and a small percentage ofalkalies. These impurities and alkalies have no harmful'efiect on thecompound, however. chloride (ALCL) is formed b t 0 aluminum of thebentoni-te and the c orine of the hydrochloric acid, and hydroussiliclcacid is formed by the splitting of the silica from thebentoniteoraluminum silicate. Dun

ing the setting period'thealuminum chloride i is adsorbed by thehydroussilicic acid "and through peptization retaining the originalbentonite structure.

In this ste aluminum moleculardispersion the liquid In this highlydispersed and highly active condition it presents a maximum surface tothe oils being treated.

Should the compound be intended for use on shale oils or other oils orfractionations having a hi h boiling point, lithium carbonate (orchloride) 'is radually added to the mixture after the addition of thehydrochloric acid. 7

If the carbonate is used, the lithia forms, in combination with thehydrochloricacid, lithium chloride -(LiCl) which is volatile only attemperatures above 600 0., while aluminumchloride, under ordinaryconditions, volatilizes at about 183 C. The lithium chloride, however,has further beneficial properties on the'compound in that we have foundit to be an excellent catalyst, even more active than the aluminumchloride, either alone or in the mixture described, and it, therefore,greatly assists the action of the colloid com ound. As little as 2 percent lithium chloride has been found to be effectual in "raising thevolatilizin point of the aluminum chloride. In addition to the effect onthe chemical properties, we have found that the addition of a smallpercentage of lithium greatly increases the colloidal properties of theclay. Hydrogen chloride gas can, ofcourse, be substituted in this1 stepfor the solution of hydrochloric ac1 (d) De-watering. The mixture isvery gradually and carefully heated to a temperature' of approximately300 C. The heating should be continued until all of the mechanicallycontained water has been driven off and all except from 3 to 5 per centof the water of constitution has been removed from the colloidalcompound. Further heating would result in driving out the hydrochloricacid and forming inactive aluminum silicate and in breaking down thestructure of, and deactivating the hydrous silicic acid. It is thereforeabsolutely essential that a small percentage of the water ofconstitution remain in the compound.

If the above described process has been carried out successfully, theresultin product is a highly porous, colloidal su stance which consistsof a peptized 0r loosely chemically-combined, or colloidally andmolecularly dispersed, aluminum chloride with a hydrous silicic-acid inthe form of a solid gel. Noaluminum chloride has been volatilized andthe material should benearly neutral and only slightly soluble.

When the above prepared compound, in granular or pulverized form, ismixed with crude petroleum or its fractionations, in phase, and thenboiled and distilled, or i the oil is passed in the vapor phase throughthe compound, it will, like anhydrous aluminum chloride, not only fcracor transform the unsaturated hydrocarbons into saturated hydro-carbons,but will according to the constitution of the crude oil and thetemperature at which it is distilled, decompose them from the heavierhydro-carbons into the lighter hydro-carbons and at the same time willdecolorize and desulphurize the product.

The most effective method of treating the oils with the improvedtreating medium has 1 been found to paw the hydrocarbon vapors through abed of the compound at the roper temperature for the fractionationsesired and at atmospheric pressure.

The above noted results in the use of the compound on the crude oilsappear to be not only due to the 'well known action of the aluminumchloride but also to the action of the hydrous .silicic acid, which isloosely combined with the aluminum chloride. The hydrous silicic acidacts as a catalyst and assists the action of the aluminum chloride andthe lithium chloride and since it has great adsorption properties forvapors and gases, it probably acts as a contact substance releasing thesulphur from the oil.

The action of the lithia in raising the volatilizing temperature of thealuminum chloride may be explained. by ionization.

Before the mineral is used, it may be activated by subjecting it tocurrent of warm air to remove hydroscopically contained water as asafeguard in case the mineral may have been exposed to moisture.

While we have described in some detail a preferred method of preparingour medium and of carrying out our process, together with the theorieswhich we believe best explain the success of the process, it isunderstood that our invention is not limited to the precise proceduredescribed nor is it dependent upon the accuracy of the theories which wehave advanced. On the contrary, our invention is not to be regarded aslimited exce t in so far as such limitations are include within theterms of the accompanying claims, in which it is our intention to claimall novelty inherent in our invention as broadly as is permissible inview of the prior art.

Having thus described our invention, what we claim and desire secured byLetters Patent is l. The use of hydrous silicic acid in combination withaluminum chloride as an oil treating medium.

2. The use of hydrous silicic acid in combination with a metal chlorideas an oil treating medium.

3. The use of a medium for the refining and distilling of oils. whichhas been prepared by the treating of an alumino-silicate clay withhydrogen chloride gas.

4. The process of preparing a medium for the refining and distilling ofoils comprismg: the treating of a natural uncalcmed a aluminum silicatewith hydrochlorie-acidto substantially the saturation point whereby thealuminum' silicate is split-mto aluminum chloride and hydrous sil'i cicacid vmechani cally combined in colloidal and molecular dispersion inthe form of a solid jelly retainlng its original structure.

5 The process of preparing a medium for the refining and distilling ofoils comprising: grindinga clay; adding suflicient water a to the groundclay to fill the pores thereof;

' ingzjgrinding a clay;

adding hydrochloric acid to the wet cla and subsequentlyremovingaportion of't e water from the clay.

6. The process ofpreparing a medium for the refining and; distillingofoils comprisadding suflicient waterv to the ground clayto-fill thepores thereof} adding hydrogen chloride gas to the wet clay; andsubsequently removing a-portion of the water from the'clay.

7. The process of preparing a medium'for the refining and distilling ofoils comprising; the treating of a natural-uncalcined aluminum silicatewith hydrochloric-acid gas, to substantially the saturation point"whereby the aluminum silicate is split into "aluminum chloride andhydrous sillcic acid 'mechanically "combined in colloidal and medium foruse in the molecular dispersion in the form of asolid jelly retainingits original structure.

8.',The step in a process of preparin a refining and distilling of oilscomprising the treatment with hyand allowing that the aluminum chloridewill be adsorbed by the hydrous silicic acid and subsequently'colloidally dispersed drogen chloride. "ga'sfofan alumina-silicate, ll

which is capable of being converted into the hydrous variety. A

hydrous silicic acid and aluminum c lo'ride 1n 'mechanlcal comblnatlon.

11, An oil treating medium comprisin aluminum chloride and hydroussiliclc and mechanically combined in colloidal and molecular dispersionin the form of a solid x 12. The recess 55pm wing amedi'um' for there inand d sti ling of oils comprls'in of-hydrochloric acid to the a diniginatura uncalcine alummum chloride and hydrous silicic acid theresultant productto age so removing-a'portion'of the containedmoisturei. a I 13. An oil treating medium com hydrous silicic acid.

tures.

HERMAN REIPNBOLDQ' HUGO-REINBOLD.

, bentonite so as to form v rising colloidally dispersed aluminumchloride. 14. An oil treating medium comprising aluminum chlorideand Intestimony whereof,- weaflix our signa-.

